WO1993001934A1

WO1993001934A1 - Concrete structure and method of fabricating said structure

Info

Publication number: WO1993001934A1
Application number: PCT/JP1992/000933
Authority: WO
Inventors: Tadami Kamaishi; Hideaki Tanisugi; Keiichi Minami; Akio Takahashi; Takashi Taniguchi; Hiroyoshi Kuramoto
Original assignee: Toray Industries, Inc.; Toray Thiokol Co., Ltd.
Priority date: 1991-07-22
Filing date: 1992-07-22
Publication date: 1993-02-04
Also published as: DE69218571T2; KR930702151A; DE69218571D1; EP0549815A4; EP0549815B1; EP0549815A1; US5447798A

Abstract

A concrete structure having a layer of mixture of concrete and polysulfide denatured epoxy resin as an intermediate layer between a concrete layer and a polysulfide denatured epoxy resin hardened layer. This concrete structure is excellent in anti-corrosive property and high in durability as well as workability, in which exceedingly high adhesiveness is created between the concrete layer and the polysulfide denatured epoxy resin hardened layer. Such a concrete structure as above can be obtained by spreading a composition containing polysulfide denatured epoxy resin on unharden concrete.

Description

Description Concrete concrete articles and method of manufacturing the same

Technical field

The present invention relates to a concrete article and a method for producing the same, and particularly to a concrete article having improved corrosion resistance and durability, which is suitable as a material for civil engineering and construction. The present invention relates to an article and a method for manufacturing the article. Background art

Principal materials for civil engineering construction include metal materials such as earth, rocks, cement, mortar, concrete, steel, etc. Molts and concretes containing gypsum as a major component are very useful in the production of various types of construction and civil engineering structures. It is inexpensive, has excellent workability, and can be easily manufactured with a free shape.The resulting concrete article shows excellent performance in terms of mechanical strength. It is the basis of material civilization.

Of such concrete articles, the present invention is directed to concrete water and sewer pipes, box scalverts, manholes, and the like. Concrete molded articles, such as tunnel walls, gutters, and various types of concrete molded articles. Resin coating 1 1 1

new It will be in a state that will be overwhelmed. Among such concrete articles, for example, regarding concrete fume pipes, concrete fume pipes are inexpensive. Although it has the advantage of high strength, it cannot be said to have good acidity and chemical resistance. Under corrosive environmental conditions, there are problems such as the inner surface of the pipe itself corroding over time, forming a fragile layer.

In order to prevent such corrosion of the pipe body, for example, a coating such as polyester resin, urethane resin, epoxy resin and acrylic resin is applied to the inner and outer surfaces of the pipe body. Coating agent and coated with the coating film, or polyvinyl chloride or polyolefin film sheet, polyester ester polyolefin resin. Non-woven fabrics and nets, such as steel, are bonded to the inner and outer surfaces of the pipe body together with a resin to form a composite with the pipe body (Japanese Patent Application Laid-Open No. 48-55553). JP-A-59-62794, JP-A-62-71614, and JP-A-63-275890.

In the above-mentioned various treatments, when a coating film is formed, the coating agent used has excellent adhesiveness to the pipe body, water resistance, and chemical resistance. In addition, the formed coating film is moderately flexible, and when a crack or the like occurs in the pipe body, it can follow the crack and close the crack. It is required to have the property of having excellent wear resistance.

However, the anticorrosion layer obtained by applying a coating agent to form a coating film is different from the concrete layer. Due to differences in thermal expansion coefficient, contraction rate, etc. of the composite pipe, it can be separated at the interface with the concrete layer, and it can fully function as a composite pipe in terms of strength and chemical resistance. I can't do that. In addition, although the corrosion-resistant layer has rigidity but is not flexible, it is not possible to close the crack by following the crack when it occurs in the pipe body. There is a problem.

In addition, in the adhesiveness of the coating agent to the concrete layer, the surface of the concrete layer on which a coating film is to be formed is a water-moisture surface. Also, even when covered with water, it is desirable to be able to form a coating film in close contact with it. However, when a coating film is formed of a commercially available epoxy resin, such as bisphenol A type epoxy resin, the resin is used in the first place. In addition to the property that adhesiveness to concrete is not so good, if water exists in the coating film forming part of concrete, It is very difficult to form a good coating film that is firmly bonded to concrete, and there is a problem that the gas barrier properties and the solvent resistance are not sufficient.

However, these resin coatings have rigidity, as described above, but are not flexible, and thus cannot sufficiently follow cracks generated in concrete. For this reason, it is conceivable to improve the crack followability by softening the resin, but this will reduce the chemical resistance and water resistance. The problem is that the wear resistance is not at a satisfactory level.

-3-New paper There is.

On the other hand, in the case of applying a sheet of various resins to a nonwoven fabric on the inner surface of the pipe body, the work involved in the process is rather complicated, and at the same time, the adhesive used for bonding the sheet to the nonwoven fabric has to be improved. However, the same problem as in the case of the coating agent at the time of forming the coating film is used, so that the adhesiveness becomes insufficient and the gas barrier property is reduced.

As described above, conventional treatments for imparting corrosion resistance to the inner and outer surfaces of concrete pipes and the like do not always provide sufficient corrosion resistance, and construction work is not always possible. If it was complicated, there was a problem.

Therefore, an object of the present invention is to provide a concrete article which has a cured polyoxysulfide resin layer excellent in adhesiveness, has excellent corrosion resistance, and has good durability. And a method for producing the same. Disclosure of the invention

The concrete article of the present invention comprises a concrete layer as an intermediate layer between the concrete layer and the cured sulfide-modified epoxy resin layer. It is characterized in that it has a mixed layer of a resin and a polysulfide-modified epoxy resin.

Further, in the method of the present invention for producing a concrete article, a composition containing a polysulfide-modified epoxy resin is applied to uncured concrete. Features this

New paper And BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a diagram showing a cured product of a polysulfide-modified epoxy resin of a concrete article according to one embodiment of the present invention, and concrete and polysulfide. Mixing with modified epoxy resin. Shows the state near the boundary with the layer. (A) is a schematic diagram showing the unevenness state by FE-SEM observation, (B) is a schematic view by SEM-XMA observation. FIG. 3 is a schematic diagram showing the amount of sulfur (S). BEST MODE FOR CARRYING OUT THE INVENTION

The concrete article of the present invention comprises a concrete and a polysulfate between a concrete layer and a polysulfide-modified epoxy resin cured layer. It has a mixed layer with an acid-modified epoxy resin.

First, each layer of the concrete article of the present invention will be described.

(a) Polysulfide-modified epoxy resin cured layer

The resin component used in the cured resin layer of the concrete article of the present invention is excellent in adhesive release strength, chemical resistance and corrosion resistance, and is suitable for water wet surface and oil surface. It has a strong adhesive force and a polysulfide skeletal structure, so it has flexibility and impact resistance. Use resin. Polysulfide denaturation Concrete articles coated with a cured epoxy resin coating have excellent corrosion resistance and follow cracks in the concrete. As a result, the overall durability is particularly improved. In addition, the coating can be applied not only to the dry surface but also to the surface where water exists, making the installation work very easy. In the case of a finished concrete article, for example a tubular body, even if the pipe wall is perforated, the excellent adhesive strength and impact resistance of the polysulfide-modified epoxy resin No coating loss in the coating. In contrast, conventional epoxy resins are brittle, so they tend to crack or break during drilling.

As the sulfide-modified epoxy resin, a resin represented by the following general formula (1) is preferable.

OI2- CH-CH2

_a ] b ^R2y - ^R4 - ^CH2 "CH-CH2… ("

(Wherein, R ¹ and R ² each represent an organic group; X and Y each represent a substituent selected from one S— group, 10— group, and one NH— group; ³ and R ⁴ each represent a residue of an epoxy prepolymer having two or more epoxy groups in the molecule, and a is an integer of 0 to 5 (however, when a = 0, X is And at least one of Y is one S-group) and b represents an integer of 1 to 50.)

The organic group of ¹ and R ^{2 in} the general formula (1) is, for example,

-CH ₂ -CH-½,-CH2 CH20 CH20 CKi CH ₂ -½,

CH ₃

(Wherein, m represents an integer of 1 or more, preferably an integer of 1 to 10).

)

And so on. In particular, it is preferable that R ¹ be —CH 2 CH 20 CH 20 CH ₂ CH ₂ 1 in terms of ease of production and physical properties of a cured product.

As R ³ and R ⁴ , for example,

~ OCH2-CH ^ OCIfc CHCH2

CH3 OH

(In the formula, n represents 1 or more, preferably an integer of 1 to 15, and R ⁵ represents H or CH _3. )

And the like.

Also, in the general formula (1), the range of the average content a of S is from 0 to 5 (however, when a = 0, at least one of X and Y is one S-group. Yes), preferably 1.5 to 2.5, and the average content b of the skeleton is in the range of 1 to 50.

Was Yes, preferably 1-30.

The compound represented by the general formula (1) is, for example, —S—group, —S—S—group, one S—S—S—group, one S—S—S—S—S —Having a sulfur-bonding group such as a group (except when a = 0), and both ends of which are 10H groups, -NH2 groups, and 1NRH groups (R is an organic group) A sulfur-containing polymer or a sulfur-containing oligomer closed with a functional group capable of reacting with an epoxy group such as an SH group;

It can be synthesized by an addition reaction with an epoxy prepolymer having two or more epoxy groups.

The epoxy prepolymer is synthesized by a condensation reaction of an aliphatic polyol with an aromatic polyol and an epichlorohydrin, and has an intramolecular structure. Having two or more epoxy groups, such as bisphenol A epoxy resin, bisphenol F epoxy resin, halogenated bisphenol A epoxy Examples thereof include a bisphenol skeleton type epoxy resin such as a resin, and an epoxy resin having a molecular structure similar to these.

In the synthesis of the compound of the above general formula (1), the above-mentioned epoxiprepolymer is used in an amount of 2 equivalents or more with respect to the sulfur-containing polymer or the sulfur-containing oligomer. In addition, it reacts.

Such polysulfide-modified epoxy resins include, for example, “FLEP—10J, 18—” manufactured by Toray Reticor Co., Ltd.

New "FLEP — 50”, “FLEP — 60” and the like.

The polysulfide-modified epoxy resin as described above may be used alone or in combination of a plurality of compounds.

The polysulfide-modified epoxy resin cured product layer is formed by mixing a curing agent with the above-described polysulfide-modified epoxy resin, applying the obtained composition to a desired portion, and then applying The coating can be formed by leaving the coating at room temperature or heating. As the curing agent, amines, acid anhydrides, and the like are mainly used. As the amines, any of a room temperature curing type, a medium temperature curing type, and a high temperature curing type can be used. Amines can be any of primary, secondary, and tertiary amines. Examples of the amines as described above include aliphatic polyamines such as triethylentetramine, dimeric acid and polyethylene polyamine. Polyamides such as condensates with benzene and aromatic polyamines such as m-xylenediamin. In addition, a modified polyamine such as an adduct of polyamine with phenyldalicydyl ether or ethylenoxide can also be used. This modified polyamine is preferred because of its low volatility and toxicity.

Examples of the acid anhydride include, for example, phthalic anhydride, hexahydrophthalic anhydride, and chlorendic acid.

New paper Can be done.

The amount of the curing agent used is determined by the epoxy equivalent of the polysulfide-modified epoxy resin (the weight of the polysulfide-modified epoxy resin per mole of epoxy group) and the terminal amino. Varies depending on the active hydrogen equivalent of the compound having a group (the weight of the compound per mole of active hydrogen).

It is preferable to use 0.7 to 1.4 times the chemical equivalent (1 mole) of active hydrogen per mole.

To these curing agents, further known curing accelerators, curing retarders and the like can be blended.

The polysulfide-modified epoxy resin includes an epoxy resin formed by polymerization of an epoxy resin added excessively at the time of its synthesis, and other epoxy resin monomers and oligomers. Or a resin compatible with a polysulfide-modified epoxy resin (for example, an alkyd resin, a polyvinyl formal, a phenolic resin, or a polyvinyl acetate). Urea resin, melamine resin, various fatty acids, etc.) in an amount of about 50% by weight or less.

In addition, if necessary, the viscosity of the mixed solution at the time of coating may be reduced to enhance the film-forming properties of the mixed solution of the polysulfide-modified epoxy resin, thereby improving the cured film. Various solvents can be added for the purpose of improving performance. Examples of the solvent include ketones such as methylethyl ketone, esters such as ethyl acetate, and chlorinated hydrocarbons such as 1,2-dichloroethane. And aromatics such as toluene and ethers such as getyl ether.

The amount of the solvent to be added is preferably about 0.5 to 500 parts by weight with respect to 100 parts by weight of the polysulfide-modified epoxy resin.

In addition, when volatilization of a solvent is a problem or when it is desired to change the performance of a cured film, various reactive diluents suitable for the purpose may be added. As such a reactive diluent, for example, those having at least one reactive epoxy group in the molecule are preferable.

Further, a pigment, a filler, a reinforcing material, and the like may be added to the above-mentioned homogeneous mixture. Examples of pigments include inorganic and organic fine powders such as talc, calcium carbonate, kaolin, polyethylene, and polystyrene, and pigments. Organic and inorganic pigments (earth, metal powder, rake, pigment, carbon, etc.), triphenylmethane, and ant Examples include soluble dyes such as laquinone-based and naphthol-based dyes.

Examples of fillers and reinforcing materials include inorganic fine powders such as cement powder, silica fume, my strength, glass flakes, asbestos, and fine aggregate. , Gravel, and polyrefin fiber

-1 1-New paper Examples include fibers, polyacrylonitrile fibers, carbon fibers, glass fibers, and woven materials such as arrowhead fibers. In particular, when used in applications where pebbles or sand or gravel flows during use, such as concrete fume pipes, shochu abrasion resistance is reduced. For the purpose of improvement, it is preferable to add a silica powder such as silica sand.

The mixing ratio of the above additives is 0.001 to 300 parts by weight for the pigment and 100 to 400 parts by weight for the extender, based on 100 parts by weight of the polysulfide modified epoxy resin. Parts and reinforcing material is preferably 0.1 to 30 parts by weight.

The above inorganic particles may be added entirely to the polysulfide-modified epoxy resin, or may be added partially to add a liquid resin to the surface of the raw concrete. After the resin is applied, the remaining amount may be added while the resin is in a liquid state, and the resin may be settled in the resin liquid by gravity or centrifugal force. A method in which a liquid resin is applied to the raw concrete surface, and the entire amount is added while the resin is in a liquid state, and the resin is settled in the resin liquid by gravity or centrifugal force. May be taken. Adding such a bulking agent is also effective in terms of cost, since it also reduces the amount of resin used.

The thickness of such a polysulfide-modified epoxy resin cured layer can be appropriately set depending on the intended use, but is preferably from 0.1 to 10 mm. Especially 0.5 ~

One 1 2-New paper Preferably it is 5 mm.

(b) Mixed layer of concrete and polysulfide modified epoxy resin

In the present invention, the mixed layer of the concrete and the polysulfide-modified epoxy resin is defined as the concrete layer and the polysulfide-modified epoxy resin cured. Although it exists as an intermediate layer with the material layer, the composition is a mixture of concrete and polysulfide-modified epoxy resin. There is no particular limitation on the composition.

The identification of the mixed layer can be performed, for example, by observing the vicinity of the fracture surface by FE-SEM and measuring the sulfur distribution by SEM-XMA.

For example, FIG. 1 shows an example of observing the morphology near the boundary between the cured polysulfide-modified epoxy resin layer and the mixed layer in one embodiment of the concrete article of the present invention. Show. In Fig. 1, (A) indicates F E — S E M (X, manufactured by Hitachi, Ltd.)

650, a microscopic scanning X-ray spectrometer) schematically shows the unevenness between the polysulfide-modified epoxy resin cured material layer and the mixed layer observed at 300x magnification using ( B) schematically shows the distribution of S when observed with a SEM-XMA (S-800, manufactured by Hitachi, Ltd., field emission electron microscope) at 300x magnification. In addition, this concrete article is coated on a 2.5 cm thick raw concrete layer with a solution of the above-described polysulfide-modified epoxy resin (polysulfur). Eid denatured epoxy

-1 3-New paper 100 parts by weight of a resin and 28 parts by weight of a curing agent) were applied to a thickness of 4 mm.

As is clear from Fig. 1, a large amount of sulfur is distributed on the polysulfide-modified epoxy resin cured product side (the area to the left of the broken line in Fig. 1 (B)). However, even beyond the boundary (broken line in Fig. 1 (B)), the distribution of sulfur does not immediately become zero, and the distribution of sulfur reaches about 120 m. Is recognized. This indicates that the polysulfide-modified epoxy resin has entered the concrete layer, that is, the polysulfide-modified epoxy resin. It can be seen that a mixed layer of the layer and the concrete layer is formed over about 120 cz m.

As described later, the polysulfide-modified epoxy resin in the mixed layer is such that the cured polysulfide-modified epoxy resin layer is a concrete layer. It is generally formed from the same resin as the polysulfide-modified epoxy resin layer because it is formed by dispersing the resin in the resin.

Also, it is preferable that the interface between the polysulfide-modified epoxy resin cured material layer and the mixed layer has irregularities as shown in Fig. 1 (A), but the degree of irregularity is higher than the boundary. It can be defined by the ratio between the length of the boundary between any two points of the above and the linear distance between the two points. In the micrograph (300 × magnification) obtained by FE-SEM near the interface, the linear distance (A) between any two points and the length of the boundary between the two points (A) B) is measured, and the degree of concavity and convexity when BA is obtained is preferably 2 to 50.

The thickness of the mixed layer of the polysulfide modified epoxy resin and the concrete as described above is preferably 5 to 500 zm, particularly 10 to 300 m. Preferably it is. If the thickness of the mixed layer is less than 5 zm, the adhesive strength will be weak, while it is difficult to exceed 500 / m due to the manufacturing method.

(c) Concrete layer

In the present invention, as the concrete layer, sand, pebbles, gravel, crushed stone, soil or clay, etc. are used as aggregates, and cement (for example, Ca) is used. O 65 weight, S i 0 ₂ 22 wt%, Al ₂ 0 3 6 wt, F e 2 0 _{3 3} wt%, using S 0 ₃ 2 etc. wt% or Rana also the name of Ru) also was added be able to. The mixing ratio of the aggregate in the concrete is preferably 40 to 90% by weight based on the solid content.

The thickness of the concrete layer as described above varies depending on its form, size, etc., but is about 1.5 to 50 cm.

Next, a method for manufacturing a concrete article of the present invention comprising the above-described layers will be described.

First, a concrete layer is formed. The form of the concrete layer is not particularly limited, and includes, for example, a fume pipe, a box scarlet, a water supply manhole, a tunnel wall, and a gutter. , Sewage masu, underground passage, etc. It can be.

For example, when forming a tubular body such as a hume tube, the raw concrete may be poured into a cylindrical pipe frame and centrifugally molded.

Next, a mixed solution (composition) containing the above-described polysulfide-modified epoxy resin is applied to the wet raw concrete immediately after molding.

As the above-mentioned coating method, a method according to the situation, such as a spraying method, a brush coating method, a dipping method, and a spraying method, can be used. When forming a cured product layer of polysulfide modified epoxy resin inside a tubular body such as a hume tube, the raw concrete is transferred to a cylindrical steel pipe frame. Into an uncured tubular body by centrifugal molding, dropping a mixture containing a polysulfide-modified epoxy resin into the tube of this tubular body, and performing centrifugal molding. It can be cast by Note that the above coating step can be performed a plurality of times as necessary.

When applying, in order to supplement the adhesiveness between the coating film and the concrete, for example, silanes such as amino silanes, urethanes, and alkoxy silanes are used. The primer may be applied to the uncured concrete surface in advance, but it is preferable to apply it directly without using a primer. Further, a cloth-like material or a mesh-like material such as a polyolefin arrowhead fiber and a polyacrylonitrile arrowhead fiber may be laminated on the inner and outer layers of the coating layer.

-1 6-/ This In this way, the raw concrete is coated with the mixture containing the polysulfide-modified epoxy resin as described above, and then the raw concrete is coated. By curing the coating and curing the coating in the process, the concrete layer contains a polysulfide modified epoxy resin. A mixed layer of concrete and polysulfide-modified epoxy resin is formed, and the concrete article of the present invention can be obtained.

Concrete object of the present invention obtained as described above

□

αο uses a polysulfide-modified epoxy resin as the coating agent for the concrete, so that the concrete layer and the resin layer A mixed layer of a unique concrete and a polysulfide-modified epoxy resin is formed between them. The reason why this mixed layer is formed is not necessarily clear. However, it is considered as follows.

(1) Since the polysulfide-modified epoxy resin contains a polysulfide bond such as an S--S bond as a repeating unit in the molecule, it is a common epoxy resin. Has a higher affinity for concrete than resin.

(2) Polysulfide-modified epoxy resin does not undergo deterioration due to water upon curing, and forms a flexible and tough coating film.

Use new - (3) Po Li sulfates § i de modified Epoxy resins, also specific gravity Ri by water is greater (about one 2 g / cm ^3.) Therefore, One by gravity or centrifugal force one 1 7 To replace the water near the surface of the raw concrete.

For the above-mentioned reasons, the structure is such that the polysulfide-modified epoxy resin is deeply rooted near the surface of the raw concrete. Is formed).

A raw concrete article coated with a polysulfide modified epoxy resin layer is further processed through a curing process such as steam curing to become a product. Even after undergoing the process, the adhesive strength of the resin to raw concrete (which cures to hardened concrete) does not decrease. The result is a much better concrete product.

In addition, the polysulfide-modified epoxy resin exhibits the following excellent properties as compared with the conventional epoxy resin. In other words, the polysulfide-modified epoxy resin contains a flexible polysulfide chain containing sulfur in the molecule, and therefore has a moderate flexibility compared to the conventional hard and brittle epoxy resin. It has excellent impact resistance and improved wear resistance. In addition, conventional epoxy resins with improved flexibility have reduced other physical properties such as chemical resistance (acid / alkali), solvent resistance, gas barrier property, etc. On the contrary, the above-mentioned properties are improved, and the sulfide-modified epoxy resin shows more excellent properties than the hard epoxy resin. These properties indicate the manufacturing process and properties of the concrete article of the present invention.

New paper It is considered that the performance was affected.

The present invention will be described in more detail with reference to the following examples. Example 1

Unit cell e n t weight 4 0 0 kg / m ³ or more, Minase e n t ratio 3 7-4 5%, the cell e n t composition was prepared in a range of scan run-flops 5 ~ 12cm, centrifugal molding After flowing into a cylindrical form (inner diameter 26 cm, length 30 cm) rotating at an acceleration of 10 G by the machine, it was cast so that it became almost uniform on the inner surface, and then further. The cement was compacted by rotating the mold for 30 minutes at a gravitational acceleration of 30 G, and a hollow raw concrete tube (thickness: 30 mm) was molded.

Next, without removing the raw concrete pipe from the formwork, rotate the formwork slowly and insert the raw concrete pipe into the inner surface of the raw concrete pipe. Polysulfide-modified epoxy resin

("FLEP-6P" manufactured by Toray Chemical Co., Ltd.) 100 parts by weight and modified aliphatic polyamine as a hardener (Daito Kogyo Co., Ltd.) The mixture (10 Og), which consisted of 28 parts by weight (Ral X—2392)) was gradually added dropwise.

After the completion of the dropping, the mold was again rotated at a gravitational acceleration of 30 G for 10 minutes, and the mixture was applied by casting onto the inner surface of the raw concrete pipe.

Subsequently, the mold was removed from the centrifugal molding machine, and cured at room temperature for 28 days until the raw concrete tube reached practical strength. After curing, the concrete is removed from the formwork.

New paper The tube was released from the mold to obtain a concrete tube having a polysulfide-modified epoxy resin cured film with a thickness of about 500 / zm on the inner surface.

An adhesion / separation test was performed on this cured film using a Kenken-type adhesion tester. As a result, all the separation of the cured film is due to the destruction of the concrete layer, and it is confirmed that the adhesion of the cured film to the concrete is extremely excellent. It has been certified.

The concrete tube was cut, and its cross-section was observed with a SEM-XMA (X-650, Hitachi, Ltd., microscopic scanning X-ray analyzer), and its composition was analyzed. When a concrete layer and a polysulfide-modified epoxy resin cured layer were bound at the boundary between the concrete layer and the polysulfide-modified epoxy resin layer, the average thickness of the concrete and poly layer was 123 m. An intermediate layer mixed with the sulfide-modified epoxy resin was confirmed.

In addition, when the coated surface of the concrete tube was immersed in a 10% sulfuric acid aqueous solution for 3 months with the coated surface at 25, no change was observed in the cured product coating. However, adhesion to concrete did not change.

Example 2

Combine 955 g of cement, 1910 g of sand, 400 g of water and 19 g of a fluidizing agent ("Cell Flow DF" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.). Thus, a cement composition was obtained. This composition is rotated on a centrifugal molding machine at an acceleration of 10 G.

New paper (Inner diameter 20 cm, length 20 cm) and cast so that the inner surface becomes almost uniform. Further increase the rotation speed, rotate the form for 10 minutes at a gravitational acceleration of 30 G, compact the cement composition, and make a hollow raw concrete tube (thickness 13). mm) was molded.

Then, without removing the raw concrete pipe from the formwork, slowly rotate the form with 2-3 G of gravitational acceleration, 100 parts by weight of a polysulfide modified epoxy resin (“FLEP — 60”, manufactured by Toray Recoal Co., Ltd.) on the inner surface of the reed tube, and a modified aliphatic resin as a curing agent Polyamine (Daito Sangyo Co., Ltd.)

200 g of a mixed solution consisting of 392 ") 28 parts by weight was gradually added dropwise.

After the completion of the dropping, the mold was again rotated at a gravitational acceleration of 30 G for 5 minutes, and the mixed solution was applied onto the inner surface of the raw concrete pipe by casting. While rotating at 30 G, quartz sand (No. 5)

440 g was added so as to be almost uniform, and the polysulfide-modified epoxy resin mixture was cured while rotating for 20 minutes after the addition.

Subsequently, the mold was removed from the centrifugal molding machine and cured at room temperature until the raw concrete tube reached practical strength (10 days). . After curing, the concrete tube is released from the mold, and a concrete hull with a polysulfide-modified epoxy resin cured coating with a thickness of about 4 mm on the inner surface One 2 1-New paper I got a tube.

The cured coating film was subjected to an adhesion / debonding test using a Kenken-type adhesion tester. As a result, the adhesive strength was 42 kgf / cm 2, and all the release of the cured film was due to the destruction of the concrete layer. The adhesiveness was extremely excellent:

The thickness of the intermediate layer obtained by cutting this concrete fume tube and observing the cross-sectional morphology by SEM-XMA as in Example 1 was 10% on average. It was 0 m.

When cutting the fume tube, the concrete layer and the resin layer were united and did not separate during cutting. Similarly, chipping and peeling did not occur when piercing the tube wall.

The linear distance between any two points on a micrograph (300 times magnification) obtained by FE-SEM (S-800, manufactured by Hitachi, Ltd., field emission electron microscope) (A) The boundary length (B) between them was measured, and the degree of unevenness (BZA) was determined. The degree of unevenness was about 3.5.

In addition, when the coated surface of the concrete tube was immersed in a 10% sulfuric acid aqueous solution for 3 months at 25, no change was observed in the cured product film. Adhesion with concrete did not change.

Example 3

In Example 2, silica sand (No. 5) was not used. Fluoride-modified epoxy resin (manufactured by Toray Recoal Co., Ltd.)

"FLEP — 60") 100 parts by weight and a modified aliphatic polyamine as a curing agent (Daito Sangyo Co., Ltd. "Die-CL X-2392") Mixture consisting of 2 8 parts by weight 2 0 0

-2 2/1-

^ Sheet paper In the same way, except that only g was coated, concrete composite fume tubes were manufactured using a centrifugal molding machine, and a polysulfate with a thickness of about 3 mm was formed on the inner surface. A concrete fume tube having a hardened film of an ion-modified epoxy resin was obtained.

The cured coating film was subjected to an adhesion / debonding test using a Kenken-type adhesion tester. As a result, the adhesive strength was 39 kgf / cm 2, and the release of the cured film was all due to the destruction of the concrete layer. It was confirmed that the adhesiveness to the surface was extremely excellent.

This concrete fume tube was cut, and the cross-sectional form was observed by SEM-XMA in the same manner as in Example 1. The average thickness of the intermediate layer was 95%. m, and the degree of unevenness at the boundary between the polysulfide-modified epoxy resin cured layer and the intermediate layer was measured by FE-SEM in the same manner as in Example 2. It was about 3.1.

In addition, when the coated surface of the concrete tube was immersed in a 10% sulfuric acid aqueous solution for 3 months under the condition of 25, no change was observed in the cured product coating. However, the adhesiveness with the concrete did not change.

Example 4

100 parts by weight of a polysulfide modified epoxy resin ("FLEP_60" manufactured by Toray Recour Co., Ltd.) and a modified aliphatic polyamine (Daito Sekisui Co., Ltd. "Dite Clar X—2 3 9 2") 28 parts by weight and methyl chloride

-2 3-New paper 250 g of a liquid mixture consisting of 20 parts by weight of silica and 5 parts by weight of silica fine particles ("Aerosil R202" manufactured by Nihon Aerogel Industry Co., Ltd.) Except for the above, a concrete hume tube was manufactured by a centrifugal molding machine in the same manner as in Example 2, and a polysulfur having a thickness of about 3.8 mm was formed on the inner surface. A concrete fume tube having a cured coating of an id modified epoxy resin was obtained.

The cured coating film was subjected to an adhesion / debonding test using a Kenken-type adhesion tester. As a result, the adhesive strength was 42 kgf / cm ^2, and the release of the cured coating was all due to the destruction of the concrete layer. It was confirmed that the adhesiveness to the sheet was extremely excellent.

The thickness of the intermediate layer was determined by cutting this concrete hume tube and observing the cross-sectional morphology by SEM-XMA in the same manner as in Example 1. It was 20 μm, and the degree of unevenness at the boundary between the cured layer of the polysulfide-modified epoxy resin and the intermediate layer was measured by FE-SEM in the same manner as in Example 2. Of course, the degree of irregularity was about 3.5.

Example 5

Mix 475 g of cement, 9555 g of sand, 200 g of water and 8 g of a fluidizer ("Cell Flow DF" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) As a result, a paint composition was obtained. This composition was poured into a box-shaped mold (length 260 mm × width 200 mm × depth 40 ram) and allowed to stand. On this moist raw concrete, poly 2 4-new paper 100 parts by weight of a sulfide-modified epoxy resin (“FLEP — 60” manufactured by Toray Recour Co., Ltd.) and a modified aliphatic polyamine as a hardener (Daito Sangyo Co., Ltd.) 250 g of a mixed solution consisting of 28 parts by weight. .

After curing this mold at room temperature for 10 days, the resin-laminated concrete piece is released from the mold, and the resin layer is about 4 mm thick. A piece of concrete laminated on the plate was obtained.

The adhesion test was carried out on the cured film of the polysulfide-modified epoxy resin of this concrete piece using a Kenken-type adhesion tester. As a result, the adhesive strength is 35 kgf / cm 2, and all of the hardened coating is due to the destruction of the concrete layer. It was confirmed that the adhesiveness was extremely excellent.

The thickness of the intermediate layer was determined by cutting this concrete hume tube and observing the cross-sectional morphology by SEM-XMA as in Example 1. It was 5 m, and the degree of unevenness was measured by the FE-SEM in the same manner as in Example 2. The degree of unevenness at the boundary between the polysulfide-modified modified epoxy resin layer and the intermediate layer was measured. Was about 3.1.

Comparative Example 1

By the same method as in Example 1, a hollow raw concrete tube (25 mm in thickness) was molded.

-25-New ¾ ^ After curing for 10 days, the inner surface between the fumes was sand-polished to remove the distance. Then, on this inner surface, a polysulfide modified epoxy resin (Toray Recoil)

100 parts by weight of "FLEP-600" manufactured by K.K.) and modified aliphatic polyamine as a hardener ("Dite Clar X" manufactured by Daito Sangyo Co., Ltd.) 200 g of a mixed solution consisting of 28 parts by weight of 28 parts by weight was centrifugally molded in the same manner as in Example 2 to obtain a polysulfide modified epoxy resin resin having a thickness of about 4 ram. Was coated. After the resin was completely cured, the cured coating was subjected to an adhesion release test using a Kenken-type adhesion tester. As a result, the adhesive strength was as low as 23 kgf / cm ^2, and the cured film was separated at the adhesive surface.

The thickness of the intermediate layer was determined by cutting this concrete fume tube and observing the cross-sectional morphology by SEM-XMA as in Example 1. The average was 2, and as in Example 2, the degree of unevenness at the boundary between the cured polysulfide-modified epoxy resin layer and the intermediate layer was measured by FE-SEM. The degree was about 1.3.

Comparative Example 2

A concrete fume tube was manufactured in the same manner as in Comparative Example 1, and the boiler was left intact without removing the inner surface of the fume tube. A composite fume tube made of concrete was manufactured by coating the sulfide-modified epoxy resin. After the resin has completely cured, the Kenken

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C, this paper An adhesion release test was performed using an adhesive tester. As a result, the adhesive strength was as low as 9 kgf / cm ^2, and the cured film broke at the adhesive interface.

The thickness of the intermediate layer was determined by cutting this concrete hume tube and observing the cross-sectional morphology by SEM-XMA as in Example 1. The average was 3 zm, and as in Example 2, the degree of unevenness at the boundary between the polysulfide-modified epoxy resin cured layer and the intermediate layer was measured by FE-SEM. The degree was about 1.5.

Comparative Example 3

In the same manner as in Example 5, the cement composition was put into a box-shaped formwork, and after this was subjected to tube curing for 10 days, a flat plate containing only concrete was obtained. On this concrete plate, 100 parts by weight of a polysulfide-modified epoxy resin (“FLEP-160” manufactured by Toray Recour Co., Ltd.) and denatured fat as a curing agent Polyamine (Daito Clar X — 2392) manufactured by Daito Sangyo Co., Ltd.) A 250-g mixture consisting of 28 parts by weight was applied, and then 10%. The tube was cured, and a polysulfide-modified epoxy resin layer having a thickness of about 4 mm was formed.

Then, the concrete flat plate on which the resin was laminated was released from the mold, and the cured coating film was subjected to an adhesion release test using a Kenken-type adhesion tester. As a result, the adhesive strength was as low as 14 kgf / cm ^2, and the cured film was broken at the adhesive interface.

Cut this concrete fume tube and cut it.

-2 1-New paper The thickness of the intermediate layer obtained by observing the surface morphology by SEM—XMA as in Example 1 was 3 μm on average, and the same as in Example 2 by FE—SEM. When the degree of unevenness at the boundary between the resulfide-modified epoxy resin cured layer and the intermediate layer was measured, the degree of unevenness was about 1.2.

Comparative Example 4

In Example 2, the resin for the resin layer formed on the inner surface of the concrete was a polysulfide-modified epoxy resin (“FLEP — 60” manufactured by Toray Recoal Co., Ltd.). ) 100 parts by weight, and 28 parts by weight of a modified aliphatic polyamine as a hardening agent ("Daito Clar X — 2392", manufactured by Daito Industries Co., Ltd.) Instead of 200 g of the mixed solution, 100 parts by weight of a wet adhesive epoxy resin (“ADEKA REGEN EPES” manufactured by Asahi Denka Kogyo Co., Ltd.) and a curing agent (Asahi Denka Kogyo ( "Adekano, one donor ER 235G")). Drop 200 g of the mixed solution consisting of 30 parts by weight on the inner surface of the raw concrete tube. A composite fume tube made of concrete is manufactured by a centrifugal molding machine in the same manner except that it is cast and applied, and has a hardened film with a thickness of about 4 mm on the inner surface. To obtain a down-click rie door made of a non-yu over beam tube.

The cured coating film was subjected to an adhesion / debonding test using a Kenken-type adhesion tester. As a result, the adhesive strength was as low as 11 kgf / cm ^2, and the release of the cured film all occurred on the adhesive surface.

In addition, the obtained hume tube was perforated in the tube wall in Example 2.

-2 8-New In the same manner as described above, the resin was separated from the concrete.

Comparative Example 5

-2 8 /-1- In Example 2, as the resin for the resin layer formed on the inner surface of the concrete, a polysulfide modified epoxy resin ("FLEP-6" manufactured by Toray Reticor Co., Ltd.) was used. 0 ") 100 parts by weight and a modified aliphatic polyamine as a hardening agent (" Daito Clar X-2392 ", manufactured by Daito Industrial Co., Ltd.) 28 parts by weight Instead of 200 g of the resulting mixture, 100 parts by weight of epoxy resin (“Epicoate 8288” manufactured by Yuka Shell Epoxy Co., Ltd.) and a curing agent (Daito Dye Krasole 1-20995 "manufactured by Sangyo Co., Ltd.) Using 200 g of a mixed solution consisting of 40 parts by weight, use this as a raw concrete tube. In the same way, a concrete hume tube made of concrete was manufactured using a centrifugal molding machine, except that it was dropped on the inner surface of the tube and cast-applied, and a hardened film with a thickness of about 4 mm was formed on the inner surface. Have con A Huit tube made by Reed was obtained.

The cured coating film was subjected to an adhesive peel test using a Kenken-type adhesion tester. As a result, the adhesive strength was as low as 2.5 kgf / cm ^2, and all the separation of the cured film occurred on the adhesive surface. Industrial applicability

In the concrete article of the present invention, since the cured film is made of polysulfide-modified epoxy resin, the film density is high, and the chemical resistance to acid and alkali and the resistance to acid and alkaline are high. Solvent properties are better than ordinary epoxy resins, gas barrier properties are good, and corrosion resistance is excellent. Therefore, this

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■ "· · '-no no fri The concrete article has excellent durability. In addition, the cured coating of this concrete article is moderately flexible, and has excellent flexibility and impact resistance. It is possible to close cracks.

In addition, since this cured coating can be easily formed on the surface wet with water or the surface of raw concrete, it is easier to perform the work on the concrete body than before. It is. Therefore, it is possible to produce a concrete article excellent in corrosion resistance and durability with high productivity.

Furthermore, in the concrete article of the present invention, a mixed layer of a borosulfide-modified epoxy resin and concrete is formed near the surface of the raw concrete. Since the polysulfide-modified epoxy resin has a deep-rooted structure, the concrete of the polysulfide-modified epoxy resin cured material layer Extremely strong adhesion to

Such concrete articles of the present invention are manufactured by concrete.These are sewer pipes, box scall nots, manholes, tunnel walls, gutters, and various types of concrete. It is suitable for concrete moldings.

One 3 0 —

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Claims

The scope of the claims

1. Between the concrete layer and the cured polysulfide-modified epoxy resin layer, concrete and polysulfide-modified epoxy resin are used as intermediate layers. A concrete article characterized by having a mixed layer with silicone resin.

2. The concrete article according to claim 1, wherein said intermediate layer has a thickness of 5 to 500 m. Goods.

3. The concrete article according to claim 1 or 2, wherein the polysulfide-modified epoxy resin has the following general formula:

(Wherein, R ¹ and R ² each represent an organic group, X and Y each represent a substituent selected from one S— group, 10— group, and one NH— group; ³ and R ⁴ each represent a residue of an epoxy prepolymer having two or more epoxi groups in the molecule, and a is an integer of 0 to 5 (however, when a = 0, X And at least one of Y is one S— group), and b represents an integer of 1 to 50.)

A concrete article characterized by being a polymer epoxy compound represented by the formula:

4. The concrete article described in claim 3

-3 1- Thus, R ^{1 in the} polysulfide-modified epoxy resin represented by the above general formula is

- CH ₂ CH ₂ 〇 CH ₂ 〇 CH ₂ CH ₂ - der is, co down click rie preparative article average value of a is characterized by the this Ru der 1.5 to 2.5.

5. The concrete article according to any one of claims 1 to 4, wherein the polysulfide-modified epoxy resin cured material layer comprises a bulking agent and Z or reinforcement. Concrete articles characterized by containing materials.

6. The concrete article according to any one of claims 1 to 5, wherein the concrete article is a fume tube. Concrete goods.

7. Between the concrete layer and the polysulfide-modified epoxy resin cured material layer, the concrete and the polysulfide-modified epoxy are used as an intermediate layer. A method for producing a concrete article having a mixed layer with a resin, comprising: a composition containing a polysulfide-modified epoxy resin in an uncured concrete. A method for producing a concrete product, characterized by being applied.

8. The method for producing a concrete article according to claim 7, wherein the intermediate layer has a thickness of 5 to 500 / m. Manufacturing method.

9. The method for producing a concrete article according to claim 7 or 8, wherein

-3 2- The epoxy resin has the following general formula

(In the formula, R ′ and R ² each represent an organic group, X and Y each represent a substituent selected from one S— group, 10— group, and one NH— group; ³ and R ⁴ each represent a residue of an epoxy prepolymer having two or more epoxi groups in the molecule, and a is an integer of 0 to 5 (however, when a = 0, X And at least one of Y is one S— group) and b represents an integer of 1 to 50.)

A method for producing a concrete article characterized by being a polymer epoxy compound represented by the formula:

10. The method for producing a concrete article according to claim 9, wherein the polysulfide-modified epoxy resin represented by the general formula is used as a base material. ? ¹ is

A method for producing a concrete article, characterized by being -CH ₂ CH ₂ OCH ₂ OCH ₂ CH _2- , wherein the average value of a is 1.5 or more and 2.5 or less.

11. The concrete article according to any one of claims 7 to 10, wherein the cured polysulfide-modified epoxy resin layer comprises a filler and / or a reinforcing material. A method for producing a concrete article characterized by containing a material.

12. The method according to any one of claims 7 to 11

-3 3- In the method of manufacturing a concrete article, a flowable raw concrete is formed into a tubular shape by a centrifugal molding method, and then a poly-solid is formed on the inner surface of the uncured concrete. A method for producing a concrete article, comprising centrifugally applying a composition containing a sulfide-modified epoxy resin.

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